Organic electroluminescent device

ABSTRACT

The present invention relates to compounds of the general formula (S-A)n-T, in which at least one fluorescent group S is linked to a phosphorescent group T via a divalent group A, to the use thereof in an electronic device, and to a formula to a formulation and an electronic device which comprise the novel compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. §371)of PCT/EP2011/005803, filed Nov. 17, 2011, which claims benefit ofGerman Application No. 10 2010 054 525.2, filed Dec. 15, 2010 which areboth incorporated by reference.

The present invention relates to compounds of the general formula(S-A)_(n)-T, in which at least one fluorescent group S is linked to aphosphorescent group via a divalent group A, to the use thereof in anelectronic device, and to a formulation and an electronic device whichcomprise the novel compounds.

Electronic devices which comprise organic, organometallic and/orpolymeric semiconductors are being used ever more frequently incommercial products or are just about to be introduced onto the market.Examples which may be mentioned here are organic-based charge-transportmaterials (in general triarylamine-based hole transporters) inphotocopiers and organic or polymeric light-emitting diodes (OLEDs orPLEDs) in display devices or organic photoreceptors in copiers. Organicsolar cells (O-SCs), organic field-effect transistors (O-FETs), organicthin-film transistors (O-TFTs), organic integrated circuits (O—ICs),organic optical amplifiers or organic laser diodes (O-lasers) are alsoat an advanced stage of development and may achieve major importance inthe future.

Many of these electronic and opto-electronic devices have, irrespectiveof the particular application, the following general layer structure,which can be adapted to the particular application:

-   -   (1) substrate,    -   (2) electrode, frequently metallic or inorganic, but also made        from organic or polymeric conductive materials;    -   (3) charge-injection layer or interlayer for compensation of        unevenness of the electrode (“planarisation layer”), frequently        made from a conductive, doped polymer,    -   (4) organic semiconductors,    -   (5) possibly a further charge-transport or charge-injection or        charge-blocking layer,    -   (6) counterelectrode, materials as mentioned under (2),    -   (7) encapsulation.

The above arrangement represents the general structure of anopto-electronic device, where various layers can be combined, so that,in the simplest case, an arrangement comprising two electrodes, betweenwhich an organic layer is located, results. The organic layer in thiscase fulfils all functions, including the emission of light. A system ofthis type is described, for example, in WO 9013148 A1 based onpoly(p-phenylenes).

A problem which arises in a “three-layer system” of this type is,however, the lack of a possibility to optimise the individualconstituents in different layers with respect to their properties, as issolved easily, for example, in the case of SMOLEDs (“small-moleculeOLEDs”) through a multilayered structure. A “small molecule OLED”consists, for example, of one or more organic hole-injection layers,hole-transport layers, emission layers, electron-transport layers andelectron-injection layers as well as an anode and a cathode, where theentire system is usually located on a glass substrate. An advantage of amultilayered structure of this type consists in that various functionsof charge injection, charge transport and emission can be divided intothe various layers and the properties of the respective layers can thusbe modified separately.

The layers in SMOLED devices are usually applied by vapour deposition ina vacuum chamber. However, this process is complex and thus expensiveand is unsuitable, in particular, for large molecules, such as, forexample, polymers, but also for many small molecules, which frequentlydecompose under the vapour-deposition conditions.

The application of layers from solution is therefore advantageous, whereboth small molecules and also oligomers or polymers can be processedfrom solution.

In the last decade, a major increase in performance occurred withrespect to the phosphorescence in SMOLEDs, in particular since the firstreport by Forrest in Nature (London) (1998), 395, p. 151. However, OLEDswhich comprise phosphorescent emitter compounds still have somedisadvantages. One disadvantage is the so-called “roll-off” effect.Owing to so-called triplet-triplet annihilation, the efficiency of thephosphorescent emission drops at high excitation densities. For thisreason, fluorescent emitter compounds are more desired in manyapplications in which high brightness is necessary. The said problem hasto date only been solved in part by so-called “phosphorescencesensitised fluorescence”. A first example of a highly efficientfluorescent SMOLED was reported by Forrest et al. in Nature (London)403[6771], 750-753. (2000), where a singlet emitter (DCM2) has beensensitised by a phosphorescent metal complex Ir(ppy)₃ in the same hostCPB, but in separate layers. It is usually assumed that in this caseenergy transfer takes place between the singlet emitter and thephosphorescent metal complex by the Förster transfer mechanism.

It is particularly desired also to achieve these effects in a singlelayer, in particular by processing this layer from solution.

In the conventional process for OLED production, both by deposition fromthe gas phase or solution-processed, it is difficult to control thedistribution of the individual components. The components usuallydistribute themselves randomly. For some physical properties of suchsystems, this is undesired, for example in the case of “phosphorescencesensitised fluorescence”. Here, in a similar manner to so-called Försterenergy transfer or Dexter energy transfer, energy is transferred fromthe phosphorescent emitter compound to the fluorescent emitter compound.

The Förster energy transfer rate can be represented theoretically, forexample, by the following equation:Γ_(DA)∝1/R ⁶,where R represents the separation between donor and acceptor. Thisseparation is usually also known as the Förster radius. In order tofacilitate efficient energy transfer, for example in accordance withFörster or Dexter, it is thus necessary to position the donor andacceptor, i.e. the two compound, the fluorescent emitter compound andthe phosphorescent emitter compound, as close as possible to oneanother, advantageously within the so-called Förster radius.

The fact that the two emitter compounds are usually distributed randomlymeans that the requisite small separation of the two emitter moleculesfrom one another (donor and acceptor) is not guaranteed to the fullextent.

A further major problem in the case of solution-based SMOLEDs is thefilm-formation property. The materials used are frequently very readilysoluble in a solvent and can be applied to the substrate, for example,by ink-jet printing. However, many materials do not exhibit goodfilm-formation properties, caused by the high mobility of the smallmolecules in the solvent.

The object of the present invention was therefore to provide novelcompounds in which two emitter molecules have the requisite smallseparation which is necessary for efficient energy transfer between theemitter molecules, so that a random distribution of the two interactingemitter molecules in a layer of an electronic device cannot be present.

The present invention provides for this purpose a compound of thefollowing formula (1):(S-A)_(n)-T  formula (1),where the symbols and indices used have the following meaning:

-   S is on each occurrence, independently of one another, a monovalent    group which includes a fluorescent emitter unit;-   T is an n-valent group which includes a phosphorescent emitter unit;-   A represents on each occurrence, independently of one another, a    single covalent bond or a divalent unit;-   n is an integer which is greater than or equal to 1.

The covalent linking of the groups S and T in the compound of theformula (1) enables the phenomenon of “phosphorescence sensitisedfluorescence” to be achieved within a single molecule. It is furthermorealso possible to adjust the energy level of the two emitter compounds insuch a way that extrafluorescence (and described by Segal, et al., inNat. Mater. 6[5], 374-378. 2007.) preferably occurs, i.e. the efficiencyof OLEDs is increased thereby.

A phosphorescent emitter unit is taken to mean a compound which exhibitsluminescence from an excited state having relatively high spinmultiplicity S+1), where the spin quantum number S is greater than orequal to 1, such as, for example, from an excited triplet state (tripletemitter, S=1), from an MLCT mixed state or a quintet state (quintetemitter, S=2). Phosphorescent compounds typically also exhibit longerluminescence decay times compared with fluorescent compounds. Suitablephosphorescent emitter units are, in particular, compounds which emitlight, preferably in the visible region, on suitable excitation and inaddition contain at least one atom having atomic numbers >38 and <84,particularly preferably >56 and <80. Preferred phosphorescence emittersare compounds which contain copper, molybdenum, tungsten, rhenium,ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, goldor europium, in particular compounds which contain iridium, platinum orcopper. Examples of the emitters described above are revealed by theapplications WO 00/7065, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614, WO 05/033244. In general, allphosphorescent complexes as are used in accordance with the prior artfor phosphorescent OLEDs and as are known to the person skilled in theart in the area of organic electroluminescence are suitable.

The phosphorescent emitter unit is preferably a metal-ligandcoordination compound. It is preferred here for A to be bonded to anatom of a ligand of the metal-ligand coordination compound T. One H atomof an atom of the ligand is preferably not present here and thecorresponding atom of the ligand forms a link to the divalent unit A atthis position.

Due to the covalent linking of the groups S and T by the divalent unitA, the compound of the formula (1) according to the invention hasexcellent energy transfer rates between the two centres S and T.

The term “energy transfer” in the present invention is taken to mean aphysical process in which energy is transferred from an excited dye(donor) to a second dye (acceptor) in a radiation-free manner, such as,for example, in the case of so-called Förster transfer (see T. Förster,“Zwischenmolekulare Energiewanderung and Fluoreszenz” [IntermolecularEnergy Migration and Fluorescence], Ann. Physic. (1948) 437, 55) orDexter transfer (See D. L. Dexter, J. Chem. Phys., (1953) 21, 836).

In a preferred embodiment of the present invention, the group Sfunctions as donor, and the group T functions as acceptor in the senseof the said energy transfer.

In a further preferred embodiment of the present invention, the group Sfunctions as acceptor, and the group T functions as donor in the senseof the said energy transfer.

The metal-ligand coordination compound preferably contains a metal Mwhich is a transition metal, a main-group metal or a lanthanide. If Mstands for a main-group metal, it preferably stands for a metal from thethird, fourth or fifth main group, in particular for tin. If M is atransition metal, it preferably stands for Ir, Ru, Os, Pt, Zn, Cu, Mo,W, Rh, Re, Au and Pd, very particularly preferably Ru, Ir, Pt and Cu. Euis preferred as lanthanide.

Preference is given to compounds of the formula (1) in which M standsfor a transition metal, in particular for a tetracoordinated, apentacoordinated or a hexacoordinated transition metal, particularlypreferably selected from the group consisting of chromium, molybdenum,tungsten, rhenium, ruthenium, osmium, rhodium, iridium, nickel,palladium, platinum, copper, silver and gold, in particular molybdenum,tungsten, rhenium, ruthenium, osmium, iridium, platinum, copper andgold. Very particular preference is given to iridium and platinum. Themetals here can be in various oxidation states. The above-mentionedmetals are preferably in the oxidation states Cr(0), Cr(II), Cr(III),Cr(IV), Cr(VI), Mo(0), Mo(II), Mo(III), Mo(IV), Mo(VI), W(O), WOO,W(III), W(IV), W(VI), Re(I), Re(II), Re(III), Re(IV), Ru(II), Ru(III),Os(II), Os(III), Os(IV), Rh(I), Rh(III), Ir(I), Ir(III), Ir(IV), Ni(0),Ni(II), Ni(IV), Pd(II), Pt(II), Pt(IV), Cu(I), Cu(II), Cu(III), Ag(I),Ag(II), Au(I), Au(III) and Au(V); very particular preference is given toMo(0), W(0), Re(I), Ru(II), Os(II), Rh(III), Ir(III), Pt(II) and Cu(I),in particular Ir(III) and Pt(II).

In a preferred embodiment of the invention, M is a tetracoordinated orhexacoordinated metal.

The ligands of the metal-ligand coordination compound are preferablymono-, bi-, tri-, tetra-, penta- or hexadentate ligands.

If M is a hexacoordinated metal, the following coordinativepossibilities exist, depending on the number m of ligands:

-   -   m=2: M is coordinated to two tridentate ligands or to one        tetradentate and one bidentate ligand or to one pentadentate and        one monodentate ligand;    -   m=3: M is coordinated to three bidentate ligands or to one        tridentate, one bidentate and one monodentate ligand or to one        tetradentate and two monodentate ligands;    -   m=4: M is coordinated to two bidentate and two monodentate        ligands or one tridentate and three monodentate ligands;    -   m=5: M is coordinated to one bidentate and four monodentate        ligands;    -   m=6: M is coordinated to 6 monodentate ligands.

It is particularly preferred if M is a hexacoordinated metal, m=3 andthe ligands are each bidentate ligands.

If M is a tetracoordinated metal, the denticity of the ligands is asfollows, depending on m, which indicates the number of ligands:

-   -   m=2: M is coordinated to two bidentate ligands or to one        tridentate and one monodentate ligand;    -   m=3: M is coordinated to one bidentate and two monodentate        ligands;    -   m=4: M is coordinated to four monodentate ligands.

It is particularly preferred if M is a tetracoordinated metal, m=2 andthe ligands are bidentate ligands.

The ligands of the metal-ligand coordination compound are preferablyneutral, monoanionic, dianionic or trianionic ligands, particularlypreferably neutral or monoanionic ligands. They can be monodentate,bidentate, tridentate, tetradentate pentadentate or hexadentate, and arepreferably bidentate, i.e. preferably have two coordination sites.

It is furthermore preferred in accordance with the invention if in eachcase at least one ligand of the metal-ligand coordination compound is abidentate ligand.

Preferred neutral, monodentate ligands of the metal-ligand coordinationcompound are selected from carbon monoxide, nitrogen monoxide,alkylcyanides, such as, for example, acetonitrile, arylcyanides, suchas, for example, benzonitrile, alkylisocyanides, such as, for example,methylisonitrile, arylisocyanides, such as, for example,benzoisonitrile, amines, such as, for example, trimethylamine,triethylamine, morpholine, phosphines, in particular halophosphines,trialkylphosphines, triarylphosphines or alkylarylphosphines, such as,for example, trifluorophosphine, trimethylphosphine,tricyclohexylphosphine, tri-tert-butylphosphine, triphenylphosphine,tris(pentafluorophenyl)phosphine, phosphites, such as, for example,trimethyl phosphite, triethyl phosphite, arsines, such as, for example,trifluoroarsine, trimethylarsine, tricyclohexylarsine,tri-tert-butylarsine, triphenylarsine, tris(pentafluorophenyl)arsine,stibines, such as, for example, trifluorostibine, trimethylstibine,tricyclohexylstibine, tri-tert-butylstibine, triphenylstibine,tris(pentafluorophenyl)stibine, nitrogen-containing heterocycles, suchas, for example, pyridine, pyridazine, pyrazine, pyrimidine, triazine,and carbenes, in particular Arduengo carbenes.

Preferred monoanionic, monodentate ligands of the metal-ligandcoordination compound are selected from hydride, deuteride, the halidesF⁻, Cl⁻, Br⁻ and I⁻, alkylacetylides, such as, for example, methyl-C≡C⁻,tert-butyl-C≡C⁻, arylacetylides, such as, for example, phenyl-C≡C⁻,cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic oraromatic alcoholates, such as, for example, methanolate, ethanolate,propanolate, isopropanolate, tert-butylate, phenolate, aliphatic oraromatic thioalcoholates, such as, for example, methanethiolate,ethanethiolate, propanethiolate, isopropanethiolate, tert-thiobutylate,thiophenolate, amides, such as, for example, dimethylamide,diethylamide, diisopropylamide, morpholide, carboxylates, such as, forexample, acetate, trifluoroacetate, propionate, benzoate, aryl groups,such as, for example, phenyl, naphthyl, and anionic, nitrogen-containingheterocycles, such as pyrrolide, imidazolide, pyrazolide. The alkylgroups in these groups are preferably C₁-C₂₀-alkyl ngroups, particularlypreferably C₁-C₁₀-alkyl groups, very particularly preferably C₁-C₄-alkylgroups. An aryl group is also taken to mean heteroaryl groups. Thesegroups are defined as below.

Preferred di- or trianionic ligands of the metal-ligand coordinationcompound are O²⁻, S²⁻, carbides, which result in coordination in theform R—C≡M, nitrenes, which result in coordination in the form R—N═M,where R generally stands for a substituent, and N³⁻.

Preferred neutral or mono- or dianionic bidentate or polydentate ligandsof the metal-ligand coordination compound are selected from diamines,such as, for example, ethylenediamine,N,N,N′,N′-tetramethylethylenediamine, propylenediamine,N,N,N′,N′-tetramethylpropylenediamine, cis- or transdiaminocyclohexane,cis- or trans-N,N,N′,N′-tetramethyldiaminocyclohexane, imines, such as,for example, 2[1-(phenylimino)ethyl]pyridine,2[1-(2-methylphenylimino)ethyl]pyridine,2[1-(2,6-di-iso-propylphenylimino)ethyl]pyridine,2[1-(methylimino)ethyl]pyridine, 2[1-(ethylimino)ethyl]pyridine,2[1-(iso-propylimino)ethyl]pyridine,2[1-(tert-butylimino)ethyl]pyridine, diimines, such as, for example,1,2-bis(methylimino)ethane, 1,2-bis(ethylimino)ethane,1,2-bis(iso-propylimino)ethane, 1,2-bis(tert-butylimino)ethane,2,3-bis(methylimino)butane, 2,3-bis(ethylimino)butane,2,3-bis(iso-propylimino)butane, 2,3-bis(tert-butylimino)butane,1,2-bis(phenylimino)ethane, 1,2-bis(2-methylphenylimino)ethane,1,2-bis(2,6-di-iso-propylphenylimino)ethane,1,2-bis(2,6-di-tert-butylphenylimino)ethane, 2,3-bis(phenylimino)butane,2,3-bis(2-methylphenylimino)butane,2,3-bis(2,6-diiso-propylphenylimino)butane,2,3-bis(2,6-di-tert-butylphenylimino)butane, heterocycles containing twonitrogen atoms, such as, for example, 2,2′-bipyridine, o-phenanthroline,diphosphines, such as, for example, bis(diphenylphosphino)methane,bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane,bis(diphenylphosphino)butane, bis(dimethylphosphino)methane,bis(dimethylphosphino)ethane, bis(dimethylphosphino)propane,bis(diethylphosphino)methane, bis(diethylphosphino)ethane,bis(diethylphosphino)propane, bis(di-tert-butylphosphino)methane,bis(ditert-butylphosphino)ethane, bis(tert-butylphosphino)propane,1,3-diketonates derived from 1,3-diketones, such as, for example,acetylacetone, benzoylacetone, 1,5-diphenylacetylacetone,dibenzoylmethane, bis(1,1,1-trifluoroacetyl)methane, 3-ketonates derivedfrom 3-ketoesters, such as, for example, ethyl acetoacetate,carboxylates derived from aminocarboxylic acids, such as, for example,pyridine-2-carboxylic acid, quinoline-2-carboxylic acid, glycine,N,N-dimethylglycine, alanine, N,N-dimethylaminoalanine, salicyliminatesderived from salicylimines, such as, for example, methylsalicylimine,ethylsalicylimine, phenylsalicylimine, dialcoholates derived fromdialcohols, such as, for example, ethylene glycol, 1,3-propylene glycol,and dithiolates derived from dithiols, such as, for example,1,2-ethylenedithiol, 1,3-propylenedithiol.

Preferred tridentate ligands are borates of nitrogen-containingheterocycles, such as, for example, tetrakis(1-imidazolyl) borate andtetrakis(1-pyrazolyl)borate.

Preference is furthermore given to bidentate monoanionic ligands of themetal-ligand coordination compound which, with the metal, have acyclometallated five-membered ring or six-membered ring having at leastone metal-carbon bond, in particular a cyclometallated five-memberedring. These are, in particular, ligands as are generally used in thearea of phosphorescent metal complexes for organic electroluminescentdevices, i.e. ligands of the phenylpyridine, naphthylpyridine,phenylquinoline, phenylisoquinoline, etc., type, each of which may besubstituted by one or more radicals R. A multiplicity of ligands of thistype is known to the person skilled in the art in the area ofphosphorescent electroluminescent devices, and he will be able to selectfurther ligands of this type. In general, the combination of two groups,as represented by the following formulae (2) to (29), is particularlysuitable for this purpose, where one group is bonded via a neutralnitrogen atom or a carbene atom and the other group is bonded via anegatively charged carbon atom or a negatively charged nitrogen atom.The ligand of the metal-ligand coordination compound can then be formedfrom the groups of the formulae (2) to (29) through these groups bondingto one another, in each case at the position denoted by #. The positionat which the groups coordinate to the metal are denoted by *.

R here is selected on each occurrence, identically or differently, fromthe group consisting of alkyl(ene), cycloalkyl(ene), alkylsilyl(ene),silyl(ene), arylsilyl(ene), alkylalkoxyalkyl(ene), arylalkoxyalkyl(ene),alkylthioalkyl(ene), phosphine, phosphine oxide, sulfone, alkylenesulfone, sulfoxide and alkylene sulfoxide, where the alkylene group ineach case has, independently of one another, 1 to 12 C atoms and whereone or more H atoms may be replaced by F, Cl, Br, I, alkyl orcycloalkyl, where one or more CH₂ may be replaced by a heteroatom, suchas NH, O or S, or an aromatic or heteroaromatic hydrocarbon radicalhaving 5 to 20 aromatic ring atoms. X stands for N or CH. Particularlypreferably a maximum of three symbols X in each group stand for N,particularly preferably a maximum of two symbols X in each group standfor N, very particularly preferably a maximum of one symbol X in eachgroup stands for N. Especially preferably all symbols X stand for CH.

Likewise preferred ligands are η⁵-cyclopentadienyl,η⁵-pentamethylcyclopentadienyl, η⁶-benzene and η⁷-cycloheptatrienyl,each of which may be substituted by one or more radicals R.

Likewise preferred ligands are 1,3,5-cis-cyclohexane derivatives, inparticular of the formula (30), 1,1,1-tri(methylene)methane derivatives,in particular of the formula (31), and 1,1,1-trisubstituted methanes, inparticular of the formulae (32) and (33),

where, in the formulae, the coordination to the metal M is depicted ineach case, R has the meaning mentioned above, and G stands, identicallyor differently on each occurrence, for O⁻, S⁻, COO⁻, P(R)₂ or N(R)₂.

The metal-ligand coordination compound T can be an anionic or cationiccomplex, but is preferably a neutral complex, so that the compound ofthe formula (1) is a neutral compound, i.e. the valence of the metal Mand the valence of the ligands of the metal-ligand coordination compoundis selected so that the charge within each coordination compound iscompensated.

T is preferably a donor, preferably selected from the group of compoundscontaining the following ligands

where:

-   R is identical or different on each occurrence and has the same    meaning as the radical R of the compound of the formula (10);-   m is on each occurrence, independently of one another, 0, 1, 2, 3 or    4;-   n is on each occurrence, independently of one another, 0, 1, or 2;-   o is on each occurrence, independently of one another, 0, 1, 2 or 3;

Very particularly preferred for the group A from the compound of theformula (1) are the compound from the group which consists of thefollowing units, which may optionally be further substituted by one ormore radicals R, where the radicals R may be identical or different andhave the meaning indicated for the compound having the formula (10).

In a further embodiment of the present invention, the group T in thecompound of the formula (1) is a metal-ligand coordination compoundwhich functions as dye, in particular as donor in the sense of the saidenergy transfer. In general, all dye metal-ligand coordination compoundsas are used in accordance with the prior art for so-called“dye-sensitized solar cells (DSSCs)” and as are known to the personskilled in the art in the area of DSSCs are suitable. These dyes arepreferably selected from the group consisting of polypyridyl complexesof transition metals, very preferably those containing ruthenium, osmiumand copper. In a further preferred embodiment of the present invention,the dye, which is a metal complex, has the general formula ML²(X)₂,where L is preferably selected from the group consisting of2,2′-bipyridyl-4,4′-dicarboxylic acids and where M is a transitionmetal, which is preferably selected from the group consisting of Ru, Os,Fe, V and Cu, and where X is selected from the group consisting ofhalides, cyanides, thiocyanates, acetylacetonates, thiacarbamates orwater substituents. Metal complexes of this type are disclosed, forexample, in J. Phys. Chem. C 09, 113, 2966-2973, US 2009/000658, WO2009/107100, WO 2009/098643, U.S. Pat. No. 6,245,988, WO 2010/055471, JP2010-084003, EP 1622178, WO 98/50393, WO 95/29924, WO 94/04497, WO92/14741, WO 91/16719.

Examples of preferred phosphorescent emitter units are shown in thefollowing table:

formula (40)

formula (41)

formula (42)

formula (43)

formula (44)

formula (45)

formula (46)

formula (47)

formula (48)

formula (49)

formula (50)

formula (51)

formula (52)

formula (53)

formula (54)

formula (55)

formula (56)

formula (57)

formula (58)

formula (59)

formula (60)

formula (61)

formula (62)

formula (63)

formula (64)

formula (65)

formula (66)

formula (67)

formula (68)

formula (69)

formula (70)

formula (71)

formula (72)

formula (73)

formula (74)

formula (75)

formula (76)

formula (77)

formula (78)

formula (79)

formula (80)

formula (81)

formula (82)

formula (83)

formula (84)

formula (85)

formula (86)

formula (87)

formula (88)

formula (89)

formula (90)

formula (91)

formula (92)

formula (93)

formula (94)

formula (95)

formula (96)

formula (97)

formula (98)

formula (99)

formula (100)

formula (101)

formula (102)

formula (103)

formula (104)

formula (105)

formula (106)

formula (107)

formula (108)

formula (109)

formula (110)

formula (111)

formula (112)

formula (113)

formula (114)

formula (115)

formula (116)

formula (117)

formula (118)

formula (119)

formula (120)

formula (121)

formula (122)

formula (123)

formula (124)

formula (125)

formula (126)

formula (127)

formula (128)

formula (129)

formula (130)

formula (131)

formula (132)

formula (133)

formula (134)

formula (135)

formula (136)

formula (137)

formula (138)

formula (139)

formula (140)

formula (141)

formula (142)

formula (143)

formula (144)

formula (145)

formula (146)

formula (147)

formula (148)

formula (149)

formula (150)

formula (151)

formula (152)

formula (153)

formula (154)

formula (155)

formula (156)

formula (157)

formula (158)

formula (159)

formula (160)

formula (161)

formula (162)

formula (163)

formula (164)

formula (165)

formula (166)

formula (167)

formula (168)

formula (169)

formula (170)

formula (171)

formula (172)

formula (173)

formula (174)

formula (175)

formula (176)

formula (177)

formula (178)

formula (179)

formula (180)

formula (181)

formula (182)

The examples listed above of a phosphorescent emitter unit represent theabove-mentioned group T here and are bonded to one or more groups A,depending on the index n. The bonding takes place through one or morehydrogen atoms not being present on the ligands and the bonding to thegroup(s) A taking place at this position.

The group S is preferably a monovalent group which contains or consistsof a fluorescent emitter unit.

A fluorescent emitter unit in the sense of this invention is, generallyconsidered, a unit which emits light, preferably in the visible region,from an excited singlet state.

The fluorescent emitter compound preferably comprises the followingcompounds: mono- or polycyclic aromatic or heteroaromatic ring systemshaving 5 to 60 aromatic ring atoms or also tolan, stilbene orbisstyrylarylene derivatives, each of which may be substituted by one ormore radicals R. Particular preference is given here to theincorporation of 1,4-phenyl, 1,4-naphthyl, 1,4- or 9,10-anthryl, 1,6-,2,7- or 4,9-pyrenyl, 3,9- or 3,10-perylenyl, 4,4′-biphenylyl,4,4″-terphenylyl, 4,4′-bi-1,1′-naphthylyl, 4,4′-tolanyl,4,4′-stilbenzyl, 4,4″-bisstyrylaryl, benzothiadiazolyl, quinoxalinyl,phenothiazinyl, phenoxazinyl, dihydrophenazinyl, bis(thiophenyl)aryl,oligo(thiophenyl), phenazinyl, rubrenyl, pentacenyl, squarinyl andquinacridonyl, which are preferably substituted, or preferablyconjugated push-pull systems (systems which are substituted by donor andacceptor substituents, or systems such as squarines or quinacridones,which are preferably substituted.

It is furthermore preferred for S to be selected from the groupconsisting of monostyrylamines, distyrylamines, tristyrylamines,tetrastyrylamines, styrylphosphines, styryl ethers, arylamines,indenofluorenamines, indenofluorenediamines and derivatives thereof.

In principle, any organic fluorescent emitter compound which is known tothe person skilled in the art in the area of organic light-emittingdiodes or organic light-emitting electrochemical cells can be employedin accordance with the invention as unit S.

The unit S in the compound of the formula (1) according to the inventionis preferably selected from the following: styrylamine derivatives,indenofluorene derivatives, polyaromatic compounds, anthracenederivatives, tetracene derivatives, xanthene derivatives, perylenederivatives, phenylene derivatives, fluorene derivatives, arylpyrenederivatives, arylenevinylene derivatives, rubrene derivatives, coumarinederivatives, rhodamine derivatives, quinacridone derivatives,dicyanomethylenepyran derivatives, thiopyran, polymethine derivatives,pyrylium and thiapyrylium salts, periflanthene derivatives,indenoperylene derivatives, bis(azinyl)imineboron compounds,bis(azinyl)methine compounds, carbostyryl compounds, monostyrylamines,distyrylamines, tristyrylamines, tetrastyrylamines, styrylphosphines,styryl ethers, arylamines, indenofluorenamines andindenofluorenediamines, benzoindenofluorenamines,benzoindenofluorenediamines, dibenzoindenofluorenamines,dibenzoindenofluorenediamines, substituted or unsubstitutedtristilbenamines, distyrylbenzene and distyrylbiphenyl derivatives,triarylamines, naphthalene derivatives, anthracene derivatives,tetracene derivatives, fluorene derivatives, periflanthene derivatives,indenoperylene derivatives, phenanthrene derivatives, perylenederivatives, pyrene derivatives, chrysene derivatives, decacyclenederivatives, coronene derivatives, tetraphenylcyclopentadienederivatives, pentaphenylcyclopentadiene derivatives, fluorenederivatives, spirofluorene derivatives, pyran derivatives, oxazonederivatives, benzoxazole derivatives, benzothiazole derivatives,benzimidazole derivatives, pyrazine derivatives, cinnamic acid esters,diketopyrrolopyrrole derivatives, and acridone derivatives.

Blue fluorescent emitter compounds as unit S can preferably bepolyaromatic compounds, such as, for example,9,10-di(2-naphthylanthracene) and other anthracene derivatives,derivatives of tetracene, xanthene, perylene, such as, for example,2,5,8,11-tetra-t-butylperylene, phenylene, for example4,4′-(bis(9-ethyl-3-carbazovinylene)-1,1′-biphenyl, fluorene,arylpyrenes (US 2006/0222886), arylenevinylenes (U.S. Pat. No.5,121,029, U.S. Pat. No. 5,130,603), derivatives of rubrene, coumarine,rhodamine, quinacridone, such as, for example, N,N′-dimethylquinacridone(DMQA), dicyanomethylenepyrane, such as, for example, 4(dicyanoethylene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyrane (DCM),thiopyrans, polymethine, pyrylium and thiapyrylium salts, periflanthene,indenoperylene, bis(azinyl)imineboron compounds (US 2007/0092753 A1),bis(azinyl)methene compounds and carbostyryl compounds.

Furthermore preferred blue fluorescent emitter compounds as unit S canbe emitters which are described in C. H. Chen et al.: “Recentdevelopments in organic electroluminescent materials” Macromol. Symp.125, (1997), 1-48 and “Recent progress of molecular organicelectroluminescent materials and devices” Mat. Sci. and Eng. R, 39(2002), 143-222.

A monostyrylamine here is a compound which contains one substituted orunsubstituted styryl group and at least one, preferably aromatic, amine.A distyrylamine is preferably a compound which contains two substitutedor unsubstituted styryl groups and at least one, preferably aromatic,amine. A tristyrylamine is preferably a compound which contains threesubstituted or unsubstituted styryl groups and at least one, preferablyaromatic, amine. A tetrastyrylamine is preferably a compound whichcontains four substituted or unsubstituted styryl groups and at leastone, preferably aromatic, amine. The styryl group is particularlypreferably a stilbene, which may be further substituted. Thecorresponding phosphines and ethers which can be employed in accordancewith the invention are defined analogously to the amines. For thepurposes of this invention, arylamine or aromatic amine denotes acompound which contains three substituted or unsubstituted aromatic orheteroaromatic ring systems bonded directly to a nitrogen atom. At leastone of these aromatic or heteroaromatic ring systems can be a condensedring. Preferred examples thereof are aromatic anthracenamines, aromaticanthracenediamines, aromatic pyrenamines, aromatic pyrenediamines,aromatic chrysenamines and aromatic chrysenediamines. An aromaticanthracenamine can be a compound in which one diarylamine group isbonded directly to an anthracene group, preferably in position 9. Anaromatic anthracenediamine can be a compound in which two diarylaminegroups are bonded directly to an anthracene group, preferably inpositions 9 and 10. Aromatic pyrenamines, pyrenediamines, chrysenaminesand chrysenediamines are defined analogously thereto, in which thediarylamine groups on the pyrene are preferably bonded in position 1 orin positions 1 and 6.

Furthermore preferred fluorescent emitter compounds areindenofluorenamines and indenofluorenediamines, for example inaccordance with WO 2006/122630, benzoindenofluorenamines andbenzoindenofluorenediamines, for example in accordance with WO2008/006449, and dibenzoindenofluorenamines anddibenzoindenofluorenediamines, for example in accordance with WO2007/140847.

Examples of further fluorescent emitter compounds from the class of thestyrylamines which can be employed in accordance with the invention aresubstituted or unsubstituted tristilbenamines or those described in WO2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549 and WO2007/115610. Distyrylbenzene and distyrylbiphenyl derivatives aredescribed in U.S. Pat. No. 5,121,029. Further styrylamines can be foundin US 2007/0122656 A1. Particularly preferred styrylamines andtriarylamines are the compounds of the formulae (183) to (188) and thosewhich are disclosed in U.S. Pat. No. 7,250,532 B2, DE 102005058557 A1,CN 1583691 A, JP 08053397 A, U.S. Pat. No. 6,251,531 B1, and US2006/210830 A.

Furthermore preferred fluorescent emitter compounds can be taken fromthe group of the triarylamines as disclosed in EP 1957606 A1 and US2008/0113101 A1.

Furthermore preferred fluorescent emitter compounds can be selected fromthe derivatives of naphthalene, anthracene, tetracene, fluorene,periflanthene, indenoperylene, phenanthrene, perylene (US 2007/0252517A1), pyrene, chrysene, decacyclene, coronene,tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene,spirofluorene, rubrene, coumarine (U.S. Pat. No. 4,769,292, U.S. Pat.No. 6,020,078, US 2007/0252517 A1), pyran, oxazone, benzoxazole,benzothiazole, benzimidazole, pyrazine, cinnamic acid esters,diketopyrrolopyrrole, acridone and quinacridone (US 2007/0252517 A1).

Of the anthracene compounds, the 9,10-substituted anthracenes, such as,for example, 9,10-diphenylanthracene and 9,10-bis(phenylethynyl)anthracene, are preferred. 1,4-Bis(9′-ethynylanthracenyl)benzene mayalso be preferred as fluorescent emitter compound.

Suitable fluorescent emitter units are furthermore the structuresdepicted in the following table, and the structures disclosed in JP06/001973, WO 2004/047499, WO 2006/098080, WO 2007/065678, US2005/0260442 and WO 2004/092111.

It is preferred for the unit S to consist of one of the said fluorescentemitter compounds. The group S here is preferably bonded to A in such away that one of the hydrogen atoms is not present and the bonding to theunit A takes place at this position.

In a further embodiment of the present invention, the group S of thecompound of the formula (1) is an absorbent group which functions asdye, in particular as acceptor in the sense of the said energy transfer.In general, all organic dyes as are used in accordance with the priorart for “organic solar cells (OPVs)” and as are known to the personskilled in the art in the area of OPVs are suitable.

Particularly preferred examples of the group S for the use of thecompound of the formula (1) in solar cells are the following:

where

-   R is on each occurrence, identically or differently, a radical which    has already been defined above for formula (10); and-   X and Y is on each occurrence, identically or differently, a radical    selected from, H. halogen, alkyl, alkoxyalkyl, alkylsilyl, silyl,    alkylalkoxyalky groups,

The divalent unit A is preferably a conjugated orconjugation-interrupting unit. The unit A is particularly preferably aconjugation-interrupting unit. This has the advantage that the energytransfer rates between the groups T and S is increased without changingthe electronic properties of T and/or S.

The conjugated unit is preferably a substituted or unsubstituted mono-or polycyclic aromatic or heteroaromatic ring system having 5 to 60aromatic ring atoms.

A conjugation-interrupting unit is taken to mean a unit which interfereswith or preferably interrupts the conjugation, i.e. a possibleconjugation of the ligands bonded to A is disrupted with or preferablyinterrupted. Conjugation in chemistry is taken to mean the overlap of aπ orbital (π=PI) with a p orbital of an sp²-hybridised (carbon) atom orfurther π orbitals. By contrast, a conjugation-interrupting unit in thesense of this application is taken to mean a unit which interferes withor preferably completely prevents such an overlap. This can take place,for example, through a unit in which the conjugation is interfered withby at least one sp³-hybridised atom, preferably carbon. Likewise, theconjugation may be destroyed by a non-sp³-hybridised atom, for exampleby N, P or Si.

The conjugation-interrupting unit is preferably selected from the groupconsisting of linear or branched C₁₋₁₂-alkylene, C₃₋₈-cycloalkylene,linear or branched mono(C₁₋₁₂-alkyl)silylene, linear or brancheddi(C₁₋₁₂-alkyl)silylene, linear or branched tri(C₁₋₁₂-alkyl)silylene, asilylene group which is substituted by one, two or three mono- orpolycyclic aromatic or heteroaromatic ring systems having 5 to 60aromatic ring atoms, linear or branched Si₁₋₅-silylene, linear orbranched C₁₋₁₂-alkyloxy-C₁₋₁₂-alkylene, linear or branchedaryl-C₁₋₁₂-alkyloxy-C₁₋₁₂-alkylene, where aryl is a mono- or polycylicaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, linear or branched C₁₋₁₂-alkylthio-C₁₋₁₂-alkylene, sulfone,linear or branched C₁₋₁₂alkylene sulfone, sulfoxide and linear orbranched C₁₋₁₂-alkylene sulfoxide, where one or more H atoms of the saidgroups may be replaced by F, Cl, Br, I, a further C₁₋₁₂-alkyl orC₃₋₈-cycloalkyl, where one or more CH₂ groups of the alkyl or cycloalkylmay be replaced by heteroatoms, such as NH, O or S, or a mono- orpolycylic aromatic or heteroaromatic ring systems having 5 to 60aromatic ring atoms, and where one or more CH₂ groups of the said groupswhich represent A may be replaced by a divalent mono- or polycyclicaromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, with the proviso that the divalent unit A is able to bond to thegroups S and T via any conceivable atom of the unit.

A particularly preferably denotes a linear or branched C₁₋₁₂-alkylene orC₁₋₁₂-alkyloxy-C₁₋₁₂-alkylene, where one or more H atoms may be replacedby F.

It is furthermore preferred for A to be a C₁₋₁₂-alkylene orC₃₋₈-cycloalkylene which is substituted by two divalent mono- orpolycyclic aromatic or heteroaromatic ring systems having 5 to 60aromatic ring atoms, and for the bonding to S to take place via anaromatic atom of the one ring system and the bonding to T to take placevia an aromatic atom of the other ring system.

A further preferably corresponds to a divalent unit of the generalformulae (240) to (254),

where Ar₁, Ar₂ and Ar₃ each, independently of one another, denote amono- or polycyclic aromatic or heteroaromatic unit having 5 to 60 ringatoms, two of the radicals R¹ to R⁴ or one of the radicals R¹ to R⁴ andone of the groups Ar₁, Ar₂ and Ar₃ have a bond to the ligands L¹ or L²of the compound of the general formula (1), and where R¹, R², R³ and R⁴each, independently of one another, denote alkyl(ene), cycloalkyl(ene),alkylsilyl(ene), silyl(ene), arylsilyl(ene), alkylalkoxyalkyl(ene),arylalkoxyalkyl(ene), alkylthioalkyl(ene), phosphine, phosphine oxide,sulfone, alkylene sulfone, sulfone oxide, alkylene sulfone oxide, wherethe alkylene group in each case, independently of one another, has 1 to12 C atoms and where one or more H atoms may be replaced by F, Cl, Br,I, alkyl or cycloalkyl, where one or more CH₂ may be replaced by aheteroatom, such as NH, O or S, or an aromatic or heteroaromatichydrocarbon radical having 5 to 20 aromatic ring atoms.

The substituents R¹ to R⁴ on the respective Ar₁, Ar₂ or Ar₃ may eitherbe adjacent to one another or one or more ring atoms may lie in between.The atoms to which the substituents R¹ to R⁴ are bonded are preferablyring atoms of the aromatic or heteroaromatic unit.

The following structures are particularly preferred for A:

where the symbols and indices have the meaning indicated in the case ofstructures (240) to (254).

The following structures, as disclosed, for example, in DE102009023156.0, are particularly preferred for A:

in which the dashed lines represent bonds to the groups S and T, and Wand Z are selected, independently of one another, from the groupconsisting of H, F, C₁₋₄₀-alkyl, C₂₋₄₀-alkenyl, C₂₋₄₀-alkynyl, asubstituted or unsubstituted aromatic or heteroaromatic hydrocarbonradical having 5 to 60 ring atoms.

The parameter n is preferably 1, 2, 3, 4 or 5, particularly preferably1, 2 or 3, even more preferably 1 or 2 and most preferably 1.

It is furthermore preferred for an emission band of the fluorescentemitter unit of the compound of the formula (1) to have an emissionmaximum in the wavelength range from 500 to 750 nm

It is likewise preferred for an absorption band of the fluorescentemitter unit of the compound of the formula (1) to have an absorptionmaximum in the wavelength range from 400 to 600 nm.

An emission band of the phosphorescent emitter unit of the compound ofthe formula (1) preferably has an emission maximum in the wavelengthrange from 400 to 600 nm.

An absorption band of the fluorescent emitter unit of the compound ofthe formula (1) preferably has a wavelength range which overlaps with anemission band of the phosphorescent emitter unit.

It is furthermore also preferred for an emission band of the fluorescentemitter unit of the compound of the formula (1) to have a wavelengthrange which overlaps with an absorption band of the phosphorescentemitter unit.

Examples of compounds of the formula (1) according to the invention arethe following:

A “C₁₋₄₀-alkyl” in the present invention is preferably taken to meanlinear, branched or cyclic alkyl groups. The linear alkyl groupspreferably have 1 to 6, 1 to 10 or 1 to 40 carbon atoms. The branched orcyclic alkyl groups preferably have 3 to 6, 3 to 10 or 3 to 40 carbonatoms. Preference is given to alkyl groups having 1 to 6, or 3 to 6carbon atoms, particularly preferably 1 to 3, or 3 carbon atoms. One ormore hydrogen atoms on these alkyl groups may be replaced by a fluorineatom. In addition, one or more of the CH₂ groups in these units may bereplaced by NR, O or S(R here is a radical selected from the groupconsisting of H and C₁₋₆-alkyl). If one or more of the CH₂ groups isreplaced by NR, O or S, it is particularly preferred for only one ofthese groups to be replaced; particularly preferably by an O atom.Examples of such compounds include the following: methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl,n-pentyl, s-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl,trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, cyclopentyl,cyclohexyl, cycloheptyl and cyclooctyl. C₁₋₄-alkyl, C₁₋₁₀-alkyl andC₁₋₂₀-alkyl are likewise taken to mean alkyl groups as defined above,with the proviso that they contain correspondingly fewer carbon atoms.

A “C₂₋₄₀-alkenyl” is taken to mean a linear alkenyl group having 2 to 40carbon atoms or a branched or cyclic alkenyl group having 3 to 40 carbonatoms. It is more preferably a group having 2 or 3 to 20, even morepreferably a group having 2 or 3 to 10 and most preferably a grouphaving 2 or 3 to 6 carbon atoms. One or more hydrogen atoms may bereplaced by a fluorine atom. In addition, one or more of the CH₂ groupsin these units may be replaced by NR, O or S (R here is a radicalselected from the group consisting of H and C₁₋₆-alkyl). If one or moreof the CH₂ groups is replaced by NR, O or S, it is particularlypreferred for only one of these groups to be replaced. Examples thereofwhich may be mentioned are ethenyl, propenyl, butenyl, pentenyl,cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyland cyclooctenyl.

A “C₂₋₄₀-alkynyl” is taken to mean a linear or branched alkynyl grouphaving 2 to 40 carbon atoms. The alkynyl group more preferably has 2 to20, even more preferably 2 to 10 and most preferably 2 to 6 carbonatoms. One or more hydrogen atoms may be replaced by a fluorine atom. Inaddition, one or more of the CH₂ groups in these units may be replacedby NR, O or S (R here is a radical selected from the group consisting ofH and C₁₋₆-alkyl). If one or more of the CH₂ groups is replaced by NR, Oor S, it is particularly preferred for only one of these groups to bereplaced. Examples thereof which may be mentioned are ethynyl, propynyl,butynyl, pentynyl, hexynyl and octynyl.

“C₁₋₁₂-alkylene” in the present invention is taken to mean a linear orbranched alkyl group as defined above, preferably having 1 to 12, morepreferably 1 to 6 and most preferably 1 to 3 carbon atoms, in which ahydrogen radical is not present and a further bond is present at thissite.

“C₃₋₈-cycloalkylene” in the present invention is taken to mean a cyclicalkyl group as defined above, preferably having 3 to 8, more preferably5 to 8 and most preferably 5 or 6 carbon atoms, in which a hydrogenradical is not present and a further bond is present at this site.

“Mono(C₁₋₁₂-alkyl)silylene” in the present invention is taken to mean an(SiH₃), (SiH₂) or (SiH) unit which is linked to a linear or branchedalkyl group (as defined above) having 1 or 3 to 12 carbon atoms, morepreferably 1 or 3 to 6 carbon atoms. This group is a divalent unit,which can bond via a C atom of an alkyl group and via the Si atom (thenSiH₂ unit) or via two C atoms of one or two alkyl groups (then SiH₃unit) or both times via the Si atom (then SiH unit). The examplesindicated above in compound “C₁₋₄₀-alkyl” also apply here to the alkylgroup present.

“Di(C₁₋₁₂-alkyl)silylene” in the present invention is taken to mean an(SiH₂), (SiH) or (Si) unit which is linked to two linear or branchedalkyl groups (as defined above) having 1 or 3 to 12 carbon atoms, morepreferably 1 or 3 to 6 carbon atoms, which are identical or different oneach occurrence. This group is a divalent unit, which can bond via a Catom of an alkyl group and via the Si atom (then SiH unit) or via two Catoms of one or two alkyl groups (then SiH₂ unit) or both times via theSi atom (then Si unit). The examples indicated above in compound“C₁₋₄₀-alkyl” also apply here to the alkyl groups present.

“Tri(C₁₋₁₂-alkyl)silylene” in the present invention is taken to mean an(SiH) or (Si) unit which is linked to three linear or branched alkylgroups (as defined above) having 1 or 3 to 12 carbon atoms, morepreferably 1 or 3 to 6 carbon atoms, which are identical or different oneach occurrence. This group is a divalent unit, which can bond via a Catom of an alkyl group and via the Si atom (then Si unit) or via two Catoms of one or two alkyl groups (then SiH unit). The examples indicatedabove in connection with the definition of “C₁₋₄₀-alkyl” also apply hereto the alkyl groups present.

A silylene group which is substituted by one, two or three mono- orpolycyclic aromatic or heteroaromatic ring systems having 5 to 60aromatic ring atoms is taken to mean an Si₁-silyl group which issubstituted by one, two or three mono- or polycyclic aromatic orheteroaromatic ring systems having 5 to 60 aromatic ring atoms. Thisgroup is a divalent group, which can bond either twice via the Si atomor once via the Si atom and once via a ring atom of the ring system orboth times via ring atoms of the ring system.

“Si₁₋₅-silylene” in the present compound is taken to mean a silyl grouphaving 1 or 3 to 5 silicon atoms, which is linear or branched. It is adivalent unit which bonds via the same or different Si atoms. Examplesthereof are monosilyl, disilyl, trisilyl, tetrasilyl and pentasilyl.

A C₁₋₄₀-alkoxy group or thio-C₁₋₄₀-alkyl group is taken to mean aC₁₋₄₀-alkyl group as defined above which is bonded via an O or S atom.

Preferred alkoxy groups are Methoxy, trifluoromethoxy, ethoxy,n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or2-methylbutoxy.

“C₁₋₁₂-alkyloxy-C₁₋₁₂-alkylene” in the present invention is taken tomean a divalent ether unit having two linear or branched alkyl groupshaving 1 or 3 to 12, more preferably 1 or 3 to 6 carbon atoms, which arebonded via an oxygen atom. The examples indicated above in connectionwith the definition of “C₁₋₄₀-alkyl” also apply here to the alkyl groupspresent. The unit is a divalent unit, which can bond either via one ortwo C atoms of the same alkyl group or via two C atoms of differentalkyl groups.

“C₁₋₁₂-alkylthio-C₁₋₁₂-alkylene” in the present invention is taken tomean a divalent thioether unit having two linear or branched alkylgroups having 1 or 3 to 12, more preferably 1 or 3 to 6 carbon atomswhich are bonded via a sulfur atom. The examples indicated above inconnection with the definition of “C₁₋₄₀-alkyl” also apply here to thealkyl groups present. The unit is a divalent unit, which can bond eithervia one or two C atoms of the same alkyl group or via two C atoms ofdifferent alkyl groups.

“Aryl-C₁₋₁₂-alkyloxy-C₁₋₁₂-alkylene” in the present invention is takento mean a divalent unit as defined above for“C₁₋₁₂-alkyloxy-C₁₋₁₂-alkylene”, where an alkyl group is substituted byan aryl which represents a mono- or polycyclic aromatic orheteroaromatic ring system having 5 to 60 aromatic ring atoms as definedbelow.

“Sulfone” in the present application is taken to mean a divalent—S(═O)₂-unit.

“C₁₋₁₂-alkylene sulfone” in the present invention is an —S(═O)₂— unitwhich is substituted by an alkylene group having 1 to 12 carbon atoms.It is a divalent unit, which can bond via a C atom of the alkylene groupand via the S atom. The disclosure made above in connection with thedefinition of “C₁₋₁₂-alkylene” also applies to the alkylene groups whichare preferred here.

“Sulfoxide” in the present invention is taken to mean a divalent —S(═O)—unit.

“C₁₋₁₂-alkylene sulfoxide” in the present invention is an —S(═O)— unitwhich is substituted by an alkylene group having 1 to 12 carbon atoms.It is a divalent unit, which can bond via a C atom of the alkylene groupand via the S atom. The disclosure made above in connection with thedefinition of “C₁₋₁₂-alkylene” also applies to the alkylene groups whichare preferred here.

A mono- or polycyclic aromatic or heteroaromatic hydrocarbon radicalpreferably contains 5 to 60, more preferably 5 to 20, most preferably 5or 6 aromatic ring atoms. If the unit is an aromatic unit, it preferablycontains 6 to 20, more preferably 6 to 10, most preferably 6 carbonatoms as ring atoms. If the unit is a heteroaromatic unit, it contains 5to 20, more preferably 5 to 10, most preferably 5 aromatic ring atoms,at least one of which is a heteroatom. The heteroatoms are preferablyselected from N, O and/or S. An aromatic or heteroaromatic unit here istaken to mean either a simple aromatic ring, i.e. benzene, or a simpleheteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc.,or a condensed aryl or heteroaryl group, for example naphthalene,anthracene, phenanthrene, quinoline, isoquinoline, benzothiophene,benzofuran and indole, etc.

Examples according to the invention of the aromatic or heteroaromatichydrocarbon radicals are accordingly: benzene, naphthalene, anthracene,phenanthrene, pyrene, chrysene, benzanthracene, perylene, naphthacene,pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, pyridine, quinoline, isoquinoline, acridine,phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene,2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene,4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine,phenoxazine, phenothiazine, fluorubin, naphthyridine, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole.

A mono- or polycyclic aromatic ring system in the sense of thisinvention is preferably taken to mean an aromatic ring system having 6to 60 carbon atoms, preferably 6 to 30, particularly preferably 6 to 10carbon atoms. An aromatic ring system in the sense of the presentinvention is intended to be taken to mean a system which does notnecessarily contain only aromatic groups, but instead in which, inaddition, a plurality of aromatic may be interrupted by a shortnon-aromatic unit (<10% of the atoms other than H, preferably <5% of theatoms other than H), such as, for example, sp³-hybridised C, O, N, etc.These aromatic ring systems may be monocyclic or polycyclic, i.e. theymay contain one ring (for example phenyl) or two or more rings, whichmay also be condensed (for example naphthyl) or covalently linked (forexample biphenyl), or contain a combination of condensed and linkedrings.

Preferred aromatic ring systems are, for example, phenyl, biphenyl,triphenyl, naphthyl, anthracyl, binaphthyl, phenanthryl,dihydrophenanthryl, pyrene, dihydropyrene, chrysene, perylene,tetracene, pentacene, benzopyrene, fluorene and indene.

A mono- or polycyclic heteroaromatic ring system in the sense of thisinvention is preferably taken to mean a heteroaromatic ring systemhaving 5 to 60 ring atoms, preferably 5 to 30, particularly preferably 5to 14 ring atoms. The heteroaromatic ring system contains at least oneheteroatom selected from N, O and S (remaining atoms are carbon). Aheteroaromatic ring system is additionally intended to be taken to meana system which does not necessarily contain only aromatic orheteroaromatic groups, but instead in which, in addition, a plurality ofaromatic or heteroaromatic groups may be interrupted by a shortnon-aromatic unit (<10% of the atoms other than H, preferably <5% of theatoms other than H), such as, for example, sp³-hybridised C, O, N, etc.These heteroaromatic ring systems may be monocyclic or polycyclic, i.e.they may contain one ring (for example pyridyl) or two or more rings,which may also be condensed or covalently linked, or contain acombination of condensed and linked rings.

Preferred heteroaromatic ring systems are, for example, 5-memberedrings, such as pyrrole, pyrazole, imidazole, 1,2,3-triazole,1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole,isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-memberedrings, such as pyridine, pyridazine, pyrimidine, pyrazine,1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine,1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensed groups, such asindole, isoindole, indolizine, indazole, benzimidazole, benzotriazole,purine, naphthimidazole, phenanthrimidazole, pyridimidazole,pyrazinimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole,anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran,isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine,benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,benzoisoquinoline, acridine, phenothiazine, phenoxazine,benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine,azacarbazole, benzocarboline, phenanthridine, phenanthroline,thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene,isobenzothiophene, dibenzothiophene, benzothiadiazothiophene orcombinations of these groups. Particular preference is given toimidazole, benzimidazole and pyridine.

The general terms “alkyl(ene)”, “cycloalkyl(ene)”, “alkylsilyl(ene)”,“arylsilyl(ene)”, “alkylalkoxyalkyl(ene)”, “arylalkoxyalkyl(ene)”,“alkylthioalkyl(ene)”, “alkylene sulfone”, “alkylene sulfoxide” aretaken to mean groups in which the aryl group is as defined above and thealkyl groups or alkylene groups each has, independently of one another,1 to 12 C atoms, where one or more H atoms may be replaced by F, Cl, Br,I, alkyl or cycloalkyl, where one or more CH₂ may be replaced by aheteroatom, such as NH, O or S, or an aromatic or heteroaromatichydrocarbon radical having 5 to 20 aromatic ring atoms.

The present invention furthermore relates to a multilayer structurewhich comprises a layer which comprises a compound of the formula (1)according to the invention.

A multilayer structure in the present invention is taken to mean amultilayer structure comprising two or more layers, which are preferablyapplied successively to a glass support. The layers may compriseindividual compounds according to the invention. It is preferred for thelayers to comprise further compounds or polymers or oligomers havingdifferent properties.

The present invention furthermore relates to a formulation, inparticular a solution, dispersion or emulsion, comprising at least onecompound of the formula (1) according to the invention and at least onesolvent. Solvents which can be employed are all conceivable ones whichare capable of dissolving the compounds according to the invention orforming a suspension with them. The following organic solvents arepreferred in accordance with the invention here—without restricting theinvention: dichloromethane, trichloromethane, monochlorobenzene,o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene,o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone,1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane,ethyl acetate, n-butyl acetate, dimethylformamide, dimethylacetamide,dimethyl sulfoxide, tetralin, decalin, indane and/or mixtures thereof.

The concentration of the compound of the formula (1) according to theinvention in the solution is preferably 0.1 to 10% by weight, morepreferably 0.5 to 5% by weight, based on the total weight of thesolution. The solution optionally also comprises one or more binders inorder to adjust the rheological properties of the solutioncorrespondingly, as described, for example, in WO 2005/055248 A1.

After appropriate mixing and ageing of the solutions, these are dividedinto one of the following categories: “full” solution, “borderline”solution or insoluble. The border line is drawn between these categorieswith reference to the solubility parameters. The corresponding valuescan be obtained from the literature, such as, for example, from“Crowley, J. D., Teague, G. S. Jr. and Lowe, J. W. Jr., Journal of PaintTechnology, 38, No. 496, 296 (1966)”.

Solvent mixtures can also be used and are identified as described in“Solvents, W. H. Ellis, Federation of Societies for Coatings Technology,pp. 9 to 10, 1986”. Processes of this type can result in a mixture ofso-called “non”-solvents which dissolve the composition, although it isdesirable to have at least one true solvent in the mixture.

A further preferred form of the formulation is an emulsion, and morepreferably a miniemulsion, which are prepared, in particular, asheterophase systems, in which stable nanodroplets of a first phase aredispersed in a second continuous phase. The present invention relates,in particular, to a miniemulsion in which the various components of thecompound according to the invention are either arranged in the samephase or in different phases. Preferred distributions are the following:

-   1) The majority of all compounds according to the invention and the    majority of all functional compounds are located in the continuous    phase;-   2) The majority of all compounds according to the invention is    located in nanodroplets and the majority of all further functional    compounds, such as, for example, the host compound, is located in    the continuous phase.

Both a miniemulsion, in which the continuous phase is a polar phase, andalso an inverse miniemulsion, in which the continuous phase is anon-polar phase, can be used in the present invention. The preferredform is a miniemulsion. In order to increase the kinetic stability ofthe emulsion, surfactants can also be admixed. The choice of thesolvents for two-phase systems, the surfactants and the processing togive a stable miniemulsion should be known to a person skilled in theart in this area on the basis of his expert knowledge or throughnumerous publications, such as, for example, a comprehensive article byLandfester in Annu. Rev, Mater. Res. (06), 36, p. 231.

For use of so-called thin layers in electronic or opto-electronicdevices, the compound according to the invention or a formulationthereof can be deposited by a correspondingly suitable process. Liquidcoating of devices, such as, for example, of OLEDs, is more desirablethan vacuum deposition techniques. Deposition methods from solution areparticularly preferred. Preferred deposition techniques include, withoutcorrespondingly restricting the invention, dip coating, spin coating,ink-jet printing, letterpress printing, screen printing, doctor blaidcoating, roller printing, reverse roller printing, offset lithography,flexographic printing, web printing, spray coating, brush coating or padprinting and slot-die coating. Ink-jet printing is particularlypreferred and enables the production of high-resolution displays.

The solutions according to the invention can be applied to prefabricateddevice substrates with the aid of ink-jet printing or bymicrodispensing. To this end, preference is given to the use ofindustrial piezoelectric print heads, such as from Aprion,Hitachie-Koki, Inkjet Technology, On Target Technology, Picojet,Spectra, Trident, Xaar, in order to apply the organic semiconductorlayers to a substrate. In addition, semi-industrial print heads, such asthose from Brother, Epson, Konika, Seiko Instruments, Toshiba TEC orsingle-nozzle microdispensing equipment, as manufactured, for example,by Mikrodrop and Mikrofab, can also be used.

In order that the compound according to the invention can be applied byink-jet printing or microdispensing, it should first be dissolved in asuitable solvent. The solvents must meet the above-mentionedrequirements and must not have any disadvantageous effects on the printhead selected. In addition, the solvents should have a boiling point ofabove 100° C., preferably above 140° C. and more preferably above 150°C., in order to avoid processing problems caused by drying-out of thesolution inside the print head. Besides the above-mentioned solvents,the following solvents are also suitable: substituted and unsubstitutedxylene derivatives, di-C₁₋₂-alkylformamides, substituted andunsubstituted anisoles and other phenol ether derivatives, substitutedheterocycles, such as substituted pyridines, pyrapsines, pyrimidines,pyrrolidinones, substituted and unsubstituted N,N-di-C₁₋₂-alkylanilinesand other fluorinated or chlorinated aromatic compounds.

A preferred solvent for the deposition of the compound according to theinvention by ink-jet printing comprises a benzene derivative whichcontains a benzene ring which is substituted by one or moresubstituents, in which the total number of carbon atoms of the one ormore substituents is at least three. Thus, for example, the benzenederivative may be substituted by a propyl group or three methyl groups,where in each case the total number of carbon atoms must be at leastthree. A solvent of this type enables the formation of an ink-jet liquidwhich comprises the solvent with the compound according to theinvention, and reduces or prevents clogging of the nozzles andseparation of the components during spraying. The solvent(s) can beselected from the following example list: dodecylbenzene,1-methyl-4-tert-butylbenzene, terpineollimonene, isodurol, terpinolene,cymol and dethylbenzene. The solvent may also be a solvent mixturecomprising two or more solvents, where each of the solvents preferablyhas a boiling point of greater than 100° C., more preferably greaterthan 140° C. Solvents of this type promote film formation of thedeposited layer and reduce layer errors.

The ink-jet liquid, (i.e. a mixture, preferably of solvent(s), binderand the compound according to the invention) preferably has a viscosityat 20° C. of 1 to 100 mPa·s, more preferably 1 to 50 mPa·s and mostpreferably 1 to 30 mPa·s.

The compound or formation according to the invention may additionallycomprise one or more further components, such as, for example,surface-active substances, lubricants, wetting agents, dispersants,water-repellent agents, adhesives, flow improvers, antifoaming agents,air deposition agents, diluents, which may be reactive or unreactivesubstances, assistants, colorants, dyes or pigments, sensitisers,stabilisers or inhibitors.

The invention furthermore relates to the use of the above-mentionedcompounds according to the invention in one of the electronic oropto-electronic device mentioned below, such as an organicelectroluminescent device, in particular an organic light-emittingdiode. The compounds according to the invention are preferably formedhere as or in an electroluminescent layer. A layer is preferably formedby applying a formulation according to the invention to a support andsubsequently removing the solvent.

The invention furthermore relates to the use of the above-mentionedcompounds according to the invention in an organic electroluminescentdevice. The compounds according to the invention here are preferablyformed as or in an electroluminescent layer. A layer is preferablyformed by applying a formulation according to the invention to a supportand subsequently removing the solvent.

The present invention furthermore relates to an electronic devicecomprising a compound or formulation according to the invention.

Suitable matrix materials in electronic devices are known to the personskilled in the art and can be used for the purposes of the presentinvention. Suitable matrix materials in electronic devices for compoundsof the formula (1) are, for example, CBP (N,N-biscarbazolylbiphenyl),carbazole derivatives (for example in accordance with WO 2005/039246, US2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851),azacarbazoles (for example in accordance with EP 1617710, EP 1617711, EP1731584, JP 2005/347160), ketones (for example in accordance with WO2004/093207 or in accordance with DE 102008033943), phosphine oxides,sulfoxides and sulfones (for example in accordance with WO 2005/003253),oligophenylenes, aromatic amines (for example in accordance with US2005/0069729), bipolar matrix materials (for example in accordance withWO 2007/137725), silanes (for example in accordance with WO2005/111172), 9,9-diarylfluorene derivatives (for example in accordancewith DE 102008017591), azaboroles or boronic esters (for example inaccordance with WO 2006/117052), triazine derivatives (for example inaccordance with DE 102008036982), indolocarbazole derivatives (forexample in accordance with WO 2007/063754 or WO 2008/056746),indenocarbazole derivatives (for example in accordance with theunpublished application DE 102009023155.2 and DE 102009031021.5),diazaphosphole derivatives (for example in accordance with theunpublished application DE 102009022858.6), triazole derivatives,oxazoles and oxazole derivatives, imidazole derivatives, polyarylalkanederivatives, pyrazoline derivatives, pyrazolone derivatives,distyrylpyrazine derivatives, thiopyran dioxide derivatives,phenylenediamine derivatives, tertiary aromatic amines, styrylamines,amino-substituted chalcone derivatives, indoles, hydrazone derivatives,stilbene derivatives, silazane derivatives, aromatic dimethylidenecompounds, carbodiimide derivatives, metal complexes of8-hydroxyquinoline derivatives, such as, for example, AlQ₃, the8-hydroxyquinoline complexes may also contain triarylaminophenol ligands(US 2007/0134514 A1), metal complex polysilane compounds and thiophene,benzothiophene and dibenzothiophene derivatives.

The materials can be used as pure materials or in doped form, such as,for example, CBP intrinsic or doped with BczVBi(=4,4′-(bis(9-ethyl-3-carbazovinylene)-1,1′-biphenyl).

It is furthermore preferred to use mixtures of two or more of theabove-mentioned matrix materials, in particular mixtures of anelectron-transporting material and a hole-transporting material.

Examples of preferred carbazole derivatives are mCP(=1,3-N,N-dicarbazolebenzene (=9,9′-(1,3-phenylene)bis-9H-carbazole),formula (295), US 2005/0249976), CDBP(=9,9′-(2,2′-dimethyl[1,1′-biphenyl]-4,4′-diyl)bis-9H-carbazole),1,3-bis(N,N′-dicarbazole)benzene (=1,3-bis(carbazol-9-yl)benzene), PVK(polyvinylcarbazole), 3,5-di(9H-carbazol-9-yl)biphenyl and the furthercompounds having the formula (296) to (299) depicted below (see also US2007/0128467, US 2007/0128467).

Further preferred matrix materials in the sense of the present inventionare Si tetraaryls, as disclosed, for example, in US 004/209115, US2004/0209116 US 2007/0087219, US 2007/0087219 and H. Gilman, E. A.Zuech, Chemistry&Industry (London, United Kingdom), 1960, 120,particular preference is given here to the compounds of the formulae(300) to (307).

Particularly preferred matrix materials for phosphorescent dopants arecompounds in EP 652273, DE 102009022858.6, DE 102009023155.2, WO2007/063754 and WO 2008/056746, in particular the compounds of theformulae (308) to (311).

The electronic device is preferably an organic electroluminescentdevice, preferably comprising a cathode, an anode and at least oneorganic layer, where the organic layer comprises the compound orformulation according to the invention.

As just stated, the organic layer which comprises the compound orformulation according to the invention is preferably the emitting layer.In addition, the organic electroluminescent device may comprise furtherlayers selected from in each case one or more hole-injection layers,hole-transport layers, hole-blocking layers, electron-transport layers,electron-injection layers, electron-blocking layers, charge-generationlayers and/or layers which generate organic or inorganic P/N junctions.The electroluminescent device may in addition comprise further emittinglayers. So-called interlayers, which have, for example, anexciton-blocking function, are preferably introduced between twoemitting layers. However, it should be pointed out that each of theselayers does not necessarily have to be present.

The organic electroluminescent device preferably has a planar shapeand/or is in the form of a fibre.

A fibre in the sense of the present invention is taken to mean any shapein which the ratio between length to diameter is greater than or equalto 10:1, preferably 100:1, where the shape of the cross section alongthe longitudinal axis is not important. The cross section along thelongitudinal axis may accordingly be, for example, round, oval,triangular, rectangular or polygonal. Light-emitting fibres havepreferred properties with respect to their use. Thus, they are suitable,inter alia, for use in the area of therapeutic and/or cosmeticphototherapy. Further details in this respect are described in the priorart (for example in U.S. Pat. No. 6,538,375, US 2003/0099858, BrenndanO'Connor et al. (Adv. Mater. 2007, 19, 3897-3900 and the unpublishedpatent application EP 10002558.4).

If the organic electroluminescent device comprises a plurality ofemitting layers, where at least one emitting layer comprises thecompound according to the invention, these plurality of layerspreferably have in total a plurality of emission maxima between 380 nmand 750 nm, resulting overall in white emission, i.e. various emittingcompounds which are able to fluoresce or phosphoresce are used in theemitting layers. Particular preference is given to three layer systems,where the three layers exhibit blue, green and orange or red emission,for the basic structure see, for example, WO 2005/011013.

The various layers can be applied differently for the purposes of theinvention. For example, one or more layers in the electroluminescentdevice according to the invention can be applied from solution and oneor more layers can be applied via a sublimation process, in which thematerials are applied by vapour deposition in vacuum sublimation unitsat a pressure less than 10⁻⁵ mbar, preferably less than 10⁻⁶ mbar,particularly preferably less than 10⁻⁷ mbar. It is likewise possible toapply one or more layers by means of OVPD (organic vapour phasedeposition) processes or with the aid of carrier-gas sublimation, inwhich the materials are applied at a pressure between 10⁻⁵ mbar and 1bar. A special case of this process is the OVJP (organic vapour jetprinting) process, in which the materials are applied directly through anozzle and are thus structured (for example M. S. Arnold et al., Appl.Phys. Lett. 2008, 92, 053301).

However, it is particularly preferred for one or more layers in theorganic electroluminescent device to be applied from solution, forexample by spin coating or by means of any desired printing process,such as, for example, screen printing, flexographic printing or offsetprinting. But particularly preferably LITI (laser induced thermalimaging, thermal transfer printing), or ink-jet printing. Theseprocesses are generally known to the person skilled in the art and canbe applied by him without problems to organic electroluminescentdevices.

The device usually comprises a cathode and an anode (electrodes). Theelectrodes (cathode, anode) are selected for the purposes of thisinvention in such a way that their potential corresponds as well aspossible to the potential of the adjacent organic layer in order toensure the most efficient electron or hole injection possible.

The cathode preferably comprises metal complexes, metals having a lowwork function, metal alloys or multilayered structures comprisingvarious metals, such as, for example, alkaline-earth metals, alkalimetals, main-group metals or lanthanoids (for example Ca, Ba, Mg, Al,In, Mg, Yb, Sm, etc.). In the case of multilayered structures, furthermetals which have a relatively high work function, such as, for example,Ag, may also be used in addition to the said metals, in which casecombinations of the metals, such as, for example, Ca/Ag or Ba/Ag, aregenerally used. It may also be preferred to introduce a thin interlayerof a material having a high dielectric constant between a metalliccathode and the organic semiconductor. Suitable for this purpose are,for example, alkali metal or alkaline-earth metal fluorides, but alsothe corresponding oxides (for example LiF, Li₂O, BaF₂, MgO, NaF, etc.).The layer thickness of this layer is preferably between 1 and 10 nm,more preferably between 2 and 8 nm.

The anode preferably comprises materials having a high work function.The anode preferably has a potential of greater than 4.5 eV vs. vacuum.Suitable for this purpose are on the one hand metals having a high redoxpotential, such as, for example, Ag, Pt or Au. On the other hand,metal/metal oxide electrodes (for example Al/Ni/NiO_(x), Al/PtO_(x)) mayalso be preferred. For some applications, at least one of the electrodesmust be transparent in order to enable either irradiation of the organicmaterial (O-SCs) or the coupling-out of light (OLEDs/PLEDs, O-lasers). Apreferred structure uses a transparent anode. Preferred anode materialshere are conductive mixed metal oxides. Particular preference is givento indium tin oxide (ITO) or indium zinc oxide (IZO). Preference isfurthermore given to conductive doped organic materials, in particularconductive doped polymers.

The device is correspondingly structured in a manner known per se,depending on the application, provided with contacts and finallyhermetically sealed, since the lifetime of devices of this type isdrastically shortened in the presence of water and/or air.

The organic electroluminescent device according to the invention is—in anon-restrictive manner—preferably selected from the group consisting oforganic electroluminescent devices (OLEDs), polymeric light-emittingdiodes (PLEDs), organic light-emitting electrochemical cells (OLECs),dye light-sensitive solar cells (DSSCs), organic field-effecttransistors (O-FETs), organic thin-film transistors (O-TFTs), organiclight-emitting transistors (O-LETs), organic integrated circuits(O-ICs), organic solar cells (O-SCs), organic field-quench devices(O-FQDs), light-emitting electrochemical cells (LECs), organicphotoreceptors, organic laser diodes (O-lasers), radio frequencyidentification devices (RFID), photodetectors, sensors, logic circuits,charge-injection layers, Schottky diodes, planarising layers, antistaticfilms, conductive substrates or structures, photoconductors,electrophotographic elements, organic “spintronic” devices, organicplasma-emitting devices (OPED) or organic solar concentrators.Particular preference is given to organic electroluminescent devices.

The structure of the above-mentioned electronic device is known to aperson skilled in the art in the area of electronic devices.Nevertheless, some references which disclose a detailed device structureare indicated below.

An organic plasma-emitting device is preferably a device as described byKoller et al., in Nature Photonics (08), 2, pages 684 to 687. Theso-called OPED is very similar to the OLED described above, apart fromthe fact that at least the anode or cathode should be capable ofanchoring the surface plasma on the emitting layer. It is furthermorepreferred for the OPED to comprise a compound according to theinvention.

An organic light-emitting transistor (OLET) has a very similar structureto an organic field-effect transistor, but with a bipolar material asactive layer between the source and the drain. The most recentdevelopment is revealed in a publication by Muccini et al., in NatureMaterials 9, 496 to 503 (2010). Here too, it is preferred for the OLETto comprise at least one compound according to the invention.

Electrophotographic elements comprise a substrate, an electrode and acharge-transport layer above the electrode, and optionally acharge-generation layer between the electrode and the charge-transportlayer. Regarding diverse details and variations of such devices andmaterials which can be used herein, reference is made to the book“Organic Photoreceptors for Xerography” by Marcel Dekker, Inc., Ed. byPaul M. Borsenberger & D. S. Weiss (1998). It is preferred for a deviceof this type to comprise a compound according to the invention,particularly preferably within a charge-transport layer.

A particularly preferred organic spintronic device is a spin-valvedevice, as reported by Z. H. Xiong et al., in Nature 2004 Vol. 727, page821, which comprises two ferromagnetic electrodes and an organic layerbetween the two ferromagnetic electrodes, in which at least one of theorganic layers, which comprises a compound according to the inventionand the ferromagnetic electrode, is composed of cobalt, nickel, iron oran alloy thereof, or an ReMnO₃ or CrO₂, in which Re is a rare-earthelement.

Organic light-emitting electrochemical cells (OLECs) comprise twoelectrodes and a mixture of electrode and fluorescent species inbetween, as first reported by Pei & Heeger in Science (95), 269, pages1086 to 1088. It is desired that a compound according to the inventionis used in a device of this type.

Dye-sensitised solar cells (DSSCs) comprise, in the following sequence,an electrode/a dye-sensitised TiO₂ porous thin film/an electrolyte/acounterelectrode, as first reported by O'Regan & Grätzel in Nature (91),353, pages 737 to 740. The liquid electrode may be replaced by a solidhole-transport layer, as reported in Nature (98), 395, pages 583 to 585.

Organic solar concentrators (OSC) can be used as in the report by Baldoet al., in Science 321, 226 (2008). An OSC consists of a thin film oforganic dyes, which are deposited on a glass substrate having a highrefractive index. The dye absorbs incident solar energy and re-emits itat low energy. The majority of the re-emitted photons are fullycollected by a waveguide by total internal reflection. This takes placeby means of a photovoltaic device, which is arranged at the edge of thesubstrate.

The compounds according to the invention and the devices comprising themare furthermore suitable for use in the area of phototherapeuticmeasures.

The present invention therefore furthermore relates to the use of thecompounds according to the invention and devices comprising thecompounds for the treatment, prophylaxis and diagnosis of diseases. Thepresent invention still furthermore relates to the use, of the compoundsaccording to the invention and devices comprising the compounds for thetreatment and prophylaxis of cosmetic conditions.

The present invention furthermore relates to the compounds according tothe invention for the production of devices for the therapy, prophylaxisand/or diagnosis of therapeutic diseases.

Many diseases are associated with cosmetic aspects. Thus, a patient withsevere acne in the facial area suffers not only from the medical causesand consequences of the disease, but also from the cosmetic accompanyingcircumstances.

Phototherapy or light therapy is used in many medical and/or cosmeticareas. The compounds according to the invention and the devicescomprising these compounds can therefore be employed for the therapyand/or prophylaxis and/or diagnosis of all diseases and/or in cosmeticapplications for which the person skilled in the art considers the useof phototherapy. Besides irradiation, the term phototherapy alsoincludes photodynamic therapy (PDT) and disinfection and sterilisationin general. Phototherapy or light therapy can be used for the treatmentof not only humans or animals, but also any other type of living ornon-living materials. These include, for example, fungi, bacteria,microbes, viruses, eukaryotes, prokaryonts, foods, drinks, water anddrinking water.

The term phototherapy also includes any type of combination of lighttherapy and other types of therapy, such as, for example, treatment withactive compounds. Many light therapies have the aim of irradiating ortreating exterior parts of an object, such as the skin of humans andanimals, wounds, mucous membranes, the eye, hair, nails, the nail bed,gums and the tongue. However, the treatment or irradiation according tothe invention can also be carried out inside an object in order, forexample, to treat internal organs (heart, lung, etc.) or blood vesselsor the breast.

The therapeutic and/or cosmetic areas of application according to theinvention are preferably selected from the group of skin diseases andskin-associated diseases or changes or conditions, such as, for example,psoriasis, skin ageing, skin wrinkling, skin rejuvenation, enlarged skinpores, cellulite, oily/greasy skin, folliculitis, actinic keratosis,precancerous actinic keratosis, skin lesions, sun-damaged andsun-stressed skin, crows' feet, skin ulcers, acne, acne rosacea, scarscaused by acne, acne bacteria, photomodulation of greasy/oily sebaceousglands and their surrounding tissue, jaundice, jaundice of the newborn,vitiligo, skin cancer, skin tumours, Crigler-Najjar, dermatitis, atopicdermatitis, diabetic skin ulcers and desensitisation of the skin.

Particular preference is given for the purposes of the invention to thetreatment and/or prophylaxis of psoriasis, acne, cellulite, skinwrinkling, skin ageing, icterus and vitiligo.

Further areas of application according to the invention for thecompositions and/or devices comprising the compositions according to theinvention are selected from the group of inflammatory diseases,rheumatoid arthritis, pain therapy, treatment of wounds, neurologicaldiseases and conditions, oedema, Paget's disease, primary andmetastasising tumours, connective-tissue diseases or changes, changes inthe collagen, fibroblasts and cell level originating from fibroblasts intissues of mammals, irradiation of the retina, neovascular andhypertrophic diseases, allergic reactions, irradiation of therespiratory tract, sweating, ocular neovascular diseases, viralinfections, particularly infections caused by herpes simplex or HPV(human papillomaviruses) for the treatment of warts and genital warts.

Particular preference is given for the purposes of the invention to thetreatment and/or prophylaxis of rheumatoid arthritis, viral infectionsand pain.

Further areas of application according to the invention for thecompounds and/or devices comprising the compounds according to theinvention are selected from winter depression, sleeping sickness,irradiation for improving the mood, the reduction in pain particularlymuscular pain caused by, for example, tension or joint pain, eliminationof joint stiffness and the whitening of the teeth (bleaching).

Further areas of application according to the invention for thecompounds and/or devices comprising the compounds according to theinvention are selected from the group of disinfections. The compoundsaccording to the invention and/or the devices according to the inventioncan be used for the treatment of any type of objects (non-livingmaterials) or subjects (living materials such as, for example, humansand animals) for the purposes of disinfection. This includes, forexample, the disinfection of wounds, the reduction in bacteria, thedisinfection of surgical instruments or other articles, the disinfectionof foods, of liquids, in particular water, drinking water and otherdrinks, the disinfection of mucous membranes and gums and teeth.Disinfection here is taken to mean the reduction in the livingmicrobiological causative agents of undesired effects, such as bacteriaand germs.

For the purposes of the above-mentioned phototherapy, devices containingthe compounds according to the invention preferably emit light having awavelength between 250 and 1250 nm, particularly preferably between 300and 1000 nm and especially preferably between 400 and 850 nm.

In a particularly preferred embodiment of the present invention, thecompounds according to the invention are employed in an organiclight-emitting diode (OLED) or an organic light-emitting electrochemicalcell (OLEC) for the purposes of phototherapy. Both the OLED and the OLECcan have a planar or fibre-like structure having any desired crosssection (for example round, oval, polygonal, square) with a single- ormultilayered structure. These OLECs and/or OLEDs can be installed inother devices which comprise further mechanical, adhesive and/orelectronic elements (for example battery and/or control unit foradjustment of the irradiation times, intensities and wavelengths). Thesedevices comprising the OLECs and/or OLEDs according to the invention arepreferably selected from the group comprising plasters, pads, tapes,bandages, cuffs, blankets, caps, sleeping bags, textiles and stents.

The use of the said devices for the said therapeutic and/or cosmeticpurpose is particularly advantageous compared with the prior art, sincehomogeneous irradiation of lower irradiation intensity is possible atvirtually any site and at any time of day with the aid of the devicesaccording to the invention using the OLEDs and/or OLECs. The irradiationcan be carried out as an inpatient, as an outpatient and/or by thepatient themselves, i.e. without initiation by medical or cosmeticspecialists. Thus, for example, plasters can be worn under clothing, sothat irradiation is also possible during working hours, in leisure timeor during sleep. Complex inpatient/outpatient treatments can in manycases be avoided or their frequency reduced. The devices according tothe invention may be intended for reuse or be disposable articles, whichcan be disposed of after use once, twice or three times.

Further advantages over the prior art are, for example, lower evolutionof heat and emotional aspects. Thus, newborn being treated owing tojaundice typically have to be irradiated blindfolded in an incubatorwithout physical contact with the parents, which represents an emotionalstress situation for parents and newborn. With the aid of a blanketaccording to the invention comprising the OLEDs and/or OLECs accordingto the invention, the emotional stress can be reduced significantly. Inaddition, better temperature control of the child is possible due toreduced heat production of the devices according to the inventioncompared with conventional irradiation equipment.

The present invention furthermore relates to a method for the therapy,prophylaxis and/or diagnosis of diseases, where the compounds anddevices according to the invention are used for this purpose.

The present invention furthermore relates to a method for the therapy,prophylaxis and/or diagnosis of cosmetic conditions, where the compoundsand devices according to the invention are used for this purpose.

It should be pointed out that variations of the embodiments described inthe present invention fall within the scope of this invention. Eachfeature disclosed in the present invention can, unless explicitlyexcluded, be replaced by alternative features which serve the same, anequivalent or a similar purpose. Thus, each feature disclosed in thepresent invention should, unless stated otherwise, be regarded as anexample of a generic series or as an equivalent or similar feature.

All features of the present invention can be combined with one anotherin any way, unless certain features and/or steps are mutually exclusive.This applies, in particular, to preferred features of the presentinvention. Equally, features of non-essential combinations can be usedseparately (and not in combination).

It should furthermore be pointed out that many of the features, and inparticular those of the preferred embodiments of the present invention,should be regarded as inventive themselves and not merely as part of theembodiments of the present invention. Independent protection may begranted for these features in addition or as an alternative to eachinvention claimed at present.

The teaching regarding technical action disclosed with the presentinvention can be abstracted and combined with other examples.

The invention is explained in greater detail by the following exampleswithout wishing it to be restricted thereby.

SYNTHESIS- AND EXAMPLES

The following materials were used in this invention:

S1 (DCM) is a laser dye, purchased from Lambda Physik AG, D-37079Goettingen, Germany.

S2 (N,N′-bis(2,6-dimethylphenyl)perylene-3,4,9,10-tetracarxylic aciddiimide) is a dye for solar cells and was purchased from Sigma-Aldrichwith product No. 14799.

T1 (Flrpic) is a blue triplet emitter, and was purchased fromLuminescence Technology Corp. Taiwan, R.O. China.

T2 is a green triplet emitter, and was synthesised in accordance with J.Am. Chem. Soc. Vol 123, 4304 (2001).

TMM-080 and TMM-102 are the matrix materials from Merck KGaA. These weremixed 1:1 as matrix.

Example 1 Syntheses the Compounds E1 & E2

Compound (I) is synthesised in accordance with Patent Specification WO2005/121274

2-(2-{(E)-2-[8-(4-Iodophenyl)-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]-quinolin-9-yl]vinyl}-6-methylpyran-4-ylidene)malononitrile2

50 g (99 mmol) of compound (I) are dissolved in 500 ml ofdichloromethane and cooled to 0° C. and carefully degassed. 100 ml of a1 M HCl solution in dichloromethane are subsequently added to thereaction mixture, which is then stirred at 0° C. for 2 h. The solutionis warmed to room temperature, and a saturated Na₂S₂O₃ is carefullyadded until the reddish coloration has disappeared. The phases aresubsequently separated. The aqueous phase is extracted three times withdichloromethane, the combined organic phases are subsequently washedtwice with water, dried over magnesium sulfate, filtered, and thesolvent is stripped off in vacuo. The residue is recrystallised fromisopropanol.

52.6 g (94 mmol) (95%) of a red solid are obtained in a of purity 99.7%.

Iridium Complex (III)

Compound (III) is synthesised in accordance with patent specification JP2005/15508A.

DCM Dipehnylpyridineiridium Complex (E1)

8 g (11 mmol) of iridium complex (Ill) and 2.7 g (11 mmol) of 9-BBNdimer are dissolved in 200 ml of toluene at room temperature underprotective gas and stirred for 20 h. During the reaction, the suspensionof 9-BBN slowly dissolves. 6.1 g (11 mmol) of iodine/DCM complex and 40ml of a 1 M NaOH solution are subsequently added to the reactionsolution. The reaction mixture is carefully degassed, and 50 mg oftetrakistriphenylphosphinepalladium are added, and the mixture is heatedunder reflux for 20 h. The solution is cooled to room temperature, andthe phases are separated. The aqueous phase is extracted three timeswith toluene, the combined organic phases are subsequently washed twicewith water, dried over magnesium sulfate, filtered, and the solvent isstripped off in vacuo. The residue is recrystallised fromethanol/toluene 3:1, giving 7.2 g (6.3 mmol) (57%) of a white solidhaving a purity of 99.8%.

2-(2,6-Dimethylphenyl)-9-(4-iodo-2,6-dimethylphenyl)anthra[2,1,9-def;6,5,10-d′e′f′]diisoquinoline-1,3,8,10-tetraone 4

The tetranone (IV) is obtained by the following route as described inJournal Phys. Chem. C 2007 111 4861:

Compound (V) is synthesised in accordance with Patent Specification JP2005/15508A.

Peryleneiridium Complex E2

5 g (7.2 mmol) of iridium complex (V) and 1.8 g (7.2 mmol) of 9-BBNdimer are dissolved in 50 ml of toluene at room temperature underprotective gas and stirred for 20 h. During the reaction, the suspensionof 9-BBN slowly dissolves. 5.2 g (7.2 mmol) of the iodotetraone (IV) and20 ml of a 1 M NaOH solution are subsequently added to the reactionsolution. The reaction mixture is carefully degassed, and 30 mg oftetrakistriphenylphosphinepalladium are added, and the mixture is heatedunder reflux for 20 h. The solution is cooled to room temperature, andthe phases are separated. The aqueous phase is extracted three timeswith toluene, the combined organic phases are subsequently washed twicewith water, dried over magnesium sulfate, filtered, and the solvent isstripped off in vacuo. The residue is recrystallised fromethanol/toluene 3:1, giving 4.4 g (3.2 mmol) (45%) of a white solidhaving a purity of 99.6%.

Example 2 Production and Characterisation of Organic ElectroluminescentDevices Comprising Compound E1 According to the Invention

The production of an organic light-emitting diode from solution hasalready been described many times in the literature (for example in WO2004/037887 A2). In order to explain the present invention by way ofexample, OLEDs with various combinations of S1, T1 and E1 in matrix areproduced by means of spin coating. A typical OLED device has a layerstructure: ITO/HIL/interlayer/EML/cathode, where HIL is also calledbuffer layer.

To this end, use is made of substrates from Technoprint (soda-limeglass) to which the ITO structure (indium tin oxide, a transparent,conductive anode) is applied.

The substrates are cleaned in a clean room with deionised water and adetergent (Deconex 15 PF) and then activated by UV/ozone plasmatreatment. An 80 nm layer of PEDOT (PEDOT is a polythiophene derivative(Baytron P VAI 4083sp.) from H. C. Starck, Goslar, which is supplied asan aqueous dispersion) is then applied as buffer layer by spin coating,likewise in the clean room. The requisite spin rate depends on thedegree of dilution and the specific spin-coater geometry (typical for 80nm: 4500 rpm). In order to remove residual water from the layer, thesubstrates are dried by heating on a hotplate at 180° C. for 10 minutes.Then, under inert-gas atmosphere (nitrogen or argon), firstly 20 nm ofan interlayer (typically a hole-dominated polymer, here HIL-012 fromMerck) and then 80 nm of the emitting layers (EML for emissive layer)are applied from solutions (concentration 24 g/l in chlorobenzene, thecompositions for the various EMLs, and the concentrations thereof arelisted in Table 1). All EML layers are dried by heating at 180° C. forat least 10 minutes. The Ba/AI cathode is then applied by vapourdeposition (high-purity metals from Aldrich, particularly barium 99.99%(Order No. 474711); vapour-deposition units from Lesker or others,typical vacuum level 5×10⁶ mbar). In order to protect, in particular,the cathode against air and atmospheric moisture, the device is finallyencapsulated and then characterised.

TABLE 1 The EML compositions in various OLEDs EML Concentration DeviceEML compositions [wt %] thickness [g/l] OLED1 47.5% TMM-080:47.5% TMM-80 nm 24 012:5% S1 OLED2 47.5% TMM-080:47.5% TMM- 65 nm 24 012:5% T1OLED3 47.5% TMM-080:47.5% TMM- 80 nm 24 012:5% E1

To this end, the devices are clamped into holders manufacturedespecially for the substrate size and provided with spring contacts. Aphotodiode with eye response filter can be attached directly to themeasurement holder in order to exclude influences by extraneous light.

The voltages are typically increased from 0 to max. 20 V in 0.2 V stepsand reduced again. For each measurement point, the current through thedevice and the photocurrent obtained from the photodiode is measured. Inthis way, the IVL data of the test devices are obtained. Importantcharacteristic quantities are the measured maximum efficiency (“eff.” incd/A) and the voltage U₁₀₀ required for 100 cd/m².

In order, in addition, to know the colour and the preciseelectroluminescence spectrum of the test devices, the voltage requiredfor 100 cd/m² is again applied after the first measurement, and thephotodiode is replaced by a spectrum measuring head. This is connectedto a spectrometer (Ocean Optics) by an optical fibre. The colourcoordinates (CIE: Commission International de l'éclairage, 1931 standardobserver) can be derived from the measured spectrum.

The results obtained on use of emitters S1, T1 and E1 in OLEDs aresummarised in Table 2.

TABLE 2 Max. eff. U(100) CIE @ EQE @ Device [cd/A] [V] 100 cd/m² Max.eff. OLED1 1.26 6.4 0.61, 0.39 0.86% OLED2 1.97 6.5 0.18, 0.40 1.30%OLED3 2.80 6.5 0.61, 0.39 1.90%

As can be seen from the results, OLED3 according to the inventionrepresents a significant improvement over the two references OLED1 &OLED2 with respect to the max efficiency and EQE. On the basis of thepresent technical teaching according to the invention, furtheroptimisations can be achieved by means of various possibilities withoutbeing inventive in the process. Thus, a further optimisation can beachieved, for example, through the use of another matrix or mixedmatrices in the same or another concentration.

Example 3 Solar Cells Comprising S2 and E2

The production, measurement and characterisation of an organic solarcell from solution has already been described many times in theliterature (for example in Appl. Phys. Lett., Vol. 84, No. 19, 10 May2004, pp 3906).

Solar cells PV1 & PV2 are produced in a similar manner to OLED1-3, apartfrom:

-   -   1) the interlayer was omitted;    -   2) the EML was replaced by the active layer indicated in Table        3;    -   3) the cathode used was only 150 nm of Al.

TABLE 3 The compositions in active layer in PVs Compositions EMLConcentration PCE Device [wt %] thickness [g/l] (%) PV1 40% HIL- 200 nmapprox. 24 0.55% 012:40% PCBM:5% S2 PV2 40% HIL- 200 nm approx. 24 0.86%012:40% PCBM:5% E2

[6,6]-Phenyl C61 methyl butyrate (PCBM) was purchased fromSigma-Aldrich.

Photovoltaic characteristic lines of PV1 and PV2 are measured belowirradiation by AM1.5 (1000 W/m²). The power conversion efficiency (PCE)was calculated and listed in Table 3. By using E2, the PCE of PV1 can beimproved virtually by 40%. The possible reason for this is that with E2,photons in the blue region can also be utilised. On the basis of thepresent technical teaching according to the invention, furtheroptimisations can be achieved by means of various possibilities withoutbeing inventive in the process. Thus, a further optimisation can beachieved, for example, through the use of other hole-transport materialsor mixed matrices in the same or another concentration.

The invention claimed is:
 1. A compound of the general formula (1):(S-A)_(n)-T  formula (1), where the symbols and indices used have thefollowing meaning: S is on each occurrence, independently of oneanother, a monovalent group which includes a fluorescent emitter unit; Tis an n-valent group which includes a phosphorescent emitter unit; Arepresents on each occurrence, independently of one another, a divalentunit selected from the group consisting of divalent units of the generalformulae (240) to (254),

where Ar₁, Ar₂ and Ar₃ each, independently of one another, denote amono- or polycyclic aromatic unit having 6 to 20 ring atoms or a mono-or polycyclic heteroaromatic unit having 5 to 20 ring atoms, two of theradicals R¹ to R⁴ or one of the radicals R¹ to R⁴ and one of the groupsAr₁, Ar₂ and Ar₃ have a bond to S or T of the compound of the generalformula (1), and where R¹, R², R³ and R⁴ each, independently of oneanother, denote alkyl(ene), cycloalkyl(ene), alkylsilyl(ene),silyl(ene), arylsilyl(ene), alkylalkoxy-alkyl(ene),arylalkoxyalkyl(ene), alkylthioalkyl(ene), phosphine, phosphine oxide,sulfone, alkylene sulfone, sulfone oxide, alkylene sulfone oxide, wherethe alkylene group in each case, independently of one another, has 1 to12 C atoms and where one or more H atoms may be replaced by F, Cl, Br,I, alkyl or cycloalkyl, where one or more CH₂ is optionally replaced bya heteroatom or an aromatic or heteroaromatic hydrocarbon radical having5 to 20 aromatic ring atoms; n is 1, 2, 3, 4, or 5; wherein thephosphorescent emitter unit is a metal-ligand coordination compoundwhich includes a metal selected from the group consisting of Ir, Zn, Cu,Os, Ru, Pd, Pt, Re, Au, Mo, W, Rh and Eu and a ligand selected from thegroup consisting of formulae (34) through (39) and (34a) through (39a)

where: R is identical or different on each occurrence and is selectedfrom the group consisting of alkyl(ene), cycloalkyl(ene),alkylsilyl(ene), silyl(ene), arylsilyl(ene), alkylalkoxyalkyl(ene),arylalkoxyalkyl(ene), alkylthio-alkyl(ene), phosphine, phosphine oxide,sulfone, alkylene sulfone, sulfoxide and alkylene sulfoxide, where thealkylene group in each case has, independently of one another, 1 to 12 Catoms and where one or more H atoms is optionally replaced by F, Cl, Br,I, alkyl or cycloalkyl, where one or more CH₂ is optionally replaced byNH, O or S, or an aromatic or heteroaromatic hydrocarbon radical having5 to 20 aromatic ring atoms; m is on each occurrence, independently ofone another, 0, 1, 2, 3 or 4; n is on each occurrence, independently ofone another, 0, 1, or 2; o is on each occurrence, independently of oneanother, 0, 1, 2 or 3; wherein S is selected from the group consistingof styrylamine, indenofluorene, tetracene, xanthene, perylene,phenylene, fluorene, arylpyrene, arylenevinylene, rubrene, coumarine,rhodamine, quinacridone, dicyanomethylenepyran, thiopyran, polymethine,pyrylium and thiapyrylium salts, periflanthene, indenoperylene,bis(azinyl)imineboron compounds, bis(azinyl)methine compounds,carbostyryl compounds, monostyrylamines, distyrylamines,tristyrylamines, tetrastyrylamines, styrylphosphines, styryl ethers,arylamines, indenofluorenamines and indenofluorenediamines,benzoindenofluorenamines, benzoindenofluorenediamines,dibenzoindenofluorenamines, dibenzoindenofluorenediamines, substitutedor unsubstituted tristilbenamines, distyrylbenzene and distyrylbiphenyl,triarylamines, naphthalene, anthracene, tetracene, periflanthene,indenoperylene, phenanthrene, perylene, pyrene, chrysene, decacyclene,coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene,fluorene, spirofluorene, pyran, oxazone, benzoxazole, benzothiazole,benzimidazole, pyrazine, cinnamic acid esters, diketopyrrolopyrrole,acridone, and combinations thereof.
 2. The compound according to claim1, wherein S is selected from the group consisting of monostyrylamines,distyrylamines, tristyrylamines, tetrastyrylamines, styrylphophines,styryl ethers, arylamines, indenofluorenamines, andindenofluorenediamines.
 3. The compound according to claim 1, wherein Ais one of the following divalent units:

in which the dashed lines represent bonds to the groups S and T, and Wand Z are selected, independently of one another, from the groupconsisting of C₁₋₁₂-alkyl, a substituted or unsubstituted aromatic orheteroaromatic hydrocarbon radical having 5 to 20 ring atoms.
 4. Thecompound according to claim 1, wherein n is equal to 1, 2 or
 3. 5. Thecompound according to claim 1, wherein an emission band of thefluorescent emitter unit has an emission maximum in the wavelength rangefrom 500 to 750 nm.
 6. The compound according to claim 1, wherein anabsorption band of the fluorescent emitter unit has an absorptionmaximum in the wavelength range from 400 to 600 nm.
 7. The compoundaccording to claim 1, wherein an emission band of the phosphorescentemitter unit has an emission maximum in the wavelength range from 400 to600 nm.
 8. The compound according to claim 1, wherein an absorption bandof the fluorescent emitter unit has a wavelength range which overlapswith an emission band of the phosphorescent emitter unit.
 9. Thecompound according to claim 1, wherein an emission band of thefluorescent emitter unit has a wavelength range which overlaps with anabsorption band of the phosphorescent emitter unit.
 10. An electronicdevice which comprises the compound according to claim
 1. 11. An organicelectroluminescent device comprising the compound according to claim 1.12. The organic electroluminescent device as claimed in claim 11,wherein the device is an organic light-emitting diode, an organiclight-emitting electrochemical cell or an organic light-emittingtransistor.
 13. The electronic device according to claim 10, wherein thedevice is an organic integrated circuit, an organic field-effecttransistor, an organic thin-film transistor, an organic solar cell, adyesensitised organic solar cell, an organic optical detector, anorganic photoreceptor, an organic field-quench device, an organic laserdiode or an organic plasmon emitting device.
 14. A formulationcomprising at least one compound according to claim 1 and at least onesolvent.